US4526939A - Thermosetting coating compositions for the sealing of fiber reinforced plastics - Google Patents

Thermosetting coating compositions for the sealing of fiber reinforced plastics Download PDF

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Publication number
US4526939A
US4526939A US06/515,029 US51502983A US4526939A US 4526939 A US4526939 A US 4526939A US 51502983 A US51502983 A US 51502983A US 4526939 A US4526939 A US 4526939A
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United States
Prior art keywords
hydroxy
coating composition
recited
epoxy
resins
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Expired - Fee Related
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US06/515,029
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English (en)
Inventor
Ronald J. Lewarchik
Kevin P. Murray
Marcella G. Donovan
Arthur T. Jones
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DeSoto Inc
Valspar Corp
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DeSoto Inc
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Priority to US06/515,029 priority Critical patent/US4526939A/en
Assigned to DESOTO, INC., A DE CORP. reassignment DESOTO, INC., A DE CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: DONOVAN, MARCELLA G., JONES, ARTHUR T., LEWARCHIK, RONALD J., MURRAY, KEVIN P.
Priority to CA000450820A priority patent/CA1242829A/en
Priority to JP59102449A priority patent/JPS6028435A/ja
Priority to EP84108176A priority patent/EP0134493A3/en
Application granted granted Critical
Publication of US4526939A publication Critical patent/US4526939A/en
Assigned to VALSPAR CORPORATION, THE, A DE CORP. reassignment VALSPAR CORPORATION, THE, A DE CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: DE SOTO, INC., A CORP. OF DE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6407—Reaction products of epoxy resins with at least equivalent amounts of compounds containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/922—Polyepoxide polymer having been reacted to yield terminal ethylenic unsaturation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31525—Next to glass or quartz
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Definitions

  • This invention relates to the coating of plastic surfaces, and especially to the sealing of fiber reinforced plastics, primarily glass fiber reinforced polyester resins, and more particularly to coating compositions for this and related purposes.
  • Fiber reinforced plastic panels and moldings are well known and have diverse utility, as, for example, in automobile body parts, such as fenders, doors, and the like.
  • the exposed surface of the panel is coated with several coatings and these coatings are cured, as by baking.
  • the term moldings as used herein includes reinforced reaction injection molded compounds, which are usually polyurethanes, polyureas or polyepoxybased materials, as well as in compression molded products.
  • SMC, BMC and RRIM products are all contemplated.
  • the SMC and BMC products are glass fiber reinforced unsaturated polyester molding compounds used in sheet or bulk form, and RRIM products are the reinforced reaction injection molded compositions.
  • the exposed surface of the fiber reinforced plastic product commonly contains pores of various size and at times the coating does not adequately penetrate and fill these pores. The result is that when coatings are cured at elevated temperature, gases are released from the pores, producing blisters in the finished coatings. This problem is known as "porosity popping".
  • a prime objective herein is to fill the pores in the plastic panels before subsequent coatings are applied to provide a more chip-resistant and water-resistant coated product having a more uniform appearance as a result of avoiding or minimizing the porosity popping problem.
  • plastics such as nylon and polycarbonates and blends containing the same, exhibit poor exterior durability and/or poor resistance to moisture, disadvantages minimized by this invention.
  • the coatings herein are generally beneficial when applied to plastics which have a heat distortion temperature greater than 235° F., because this is the approximate minimum temperature needed to cure the coatings of this invention.
  • thermosetting coating compositions have been found for sealing the pores in porous fiber reinforced plastics and for other related purposes.
  • the compositions of this invention are high solids content solutions comprising one or more hydroxy functional resins, low molecular weight epoxy ester, and a curing agent having a plurality of groups reactive with the hydroxy groups in the polyester and in the epoxy ester.
  • thermosetting coating compositions of this invention are solvent solution coatings containing at least 35% solids content and comprising (1) hydroxy functional resin in an amount of from 30% to 70% of the mixture of resins, (2) from 10% to 70% of epoxy ester, and (3) the balance of the mixture of resins, but not less than about 15% of the mixture, of curing agents described hereinafter.
  • the hydroxy resin in this invention has a number average molecular weight of at least about 700 (measured by gel permeation chromatography), a viscosity less than about Z 4 Gardner bubble viscosity measured in methyl ethyl ketone at 90% solids at 25° C., and at least 5% of the hydroxy groups must be of primary character, preferably at least 50%.
  • the epoxy ester is made by esterifying one or more resinous polyepoxides having a 1,2-epoxy equivalency of at least 1.2 with an approximately stoichiometric proportion of monocarboxylic fatty acid (based on epoxy and carboxyl functionalities).
  • This essentially epoxy-free ester must have a viscosity less than Z 4 at 75% solids content in xylol using the Gardner bubble test at 25° C.
  • the preferred epoxy resins used to constitute the major proportion of the epoxy component of the epoxy ester have a molecular weight below about 1000, more preferably below 500, and most preferably have a 1,2-epoxy equivalency of from 1.7-2.0.
  • a minor proportion of the epoxy component desirably has a 1,2-epoxy equivalency in excess of 2.0, as in epoxy novalac compositions.
  • the monocarboxylic acids used for esterification desirably have from 6-22 carbon atoms, more preferably from 16-22 carbon atoms, and are most preferably unsaturated.
  • a drier salt may also be included.
  • coatings having a total solids content of from 50% up to about 90%.
  • the curing agent which is selected is broadly constituted by any known curing agent for hydroxy-functional resins, but it is preferred to employ aminoplast resins, phenoplast resins, or blocked polyisocyanates.
  • the hydroxy-functional resins used herein are subject to wide variation and may be polyethers, polyesters, polyurethanes or hydroxy-functional copolymers, all of which are well known.
  • the preferred hydroxy-functional resins are polyesters which are the polyesterification reaction products of polyesterifiable components consisting essentially of aliphatic dihydric alcohols and aliphatic dicarboxylic acids, hydroxy functionality being in excess to provide a polyester of moderate molecular weight having an acid value of less than 20, preferably less than 6, and an hydroxyl value in the range of 150-450, preferably 200-350.
  • the polyethers, polyurethanes and copolymers useful herein will generally have the same hydroxy and acid values noted for the polyesters.
  • the preferred dihydric alcohol for use in the polyesters is 1,1,3-trimethyl, 1,3-propane diol, but 1,4-butane diol and 1,6-hexane diol are also useful and illustrative of the class of C 4 -C 8 aliphatic dihydric alcohols which are useful herein.
  • Aliphatic dicarboxylic acids which may be used are C 4 -C 10 dicarboxylic acids, such as sebasic acid, adipic acid and azelaic acid. These two components should constitute at least about 85% of the polyester.
  • polyester may be constituted by an aromatic polycarboxylic acid, preferably orthophthalic anhydride or trimellitic anhydride, and this helps to provide desirable properties. This acid is coupled to the polyester through the anhydride group and it provides additional acid functionality.
  • aromatic polycarboxylic acid preferably orthophthalic anhydride or trimellitic anhydride
  • Suitable polyethers are illustrated by polyoxypropylene glycol having an average molecular weight of from 1000 to 3000.
  • Suitable polyurethanes can be provided by reacting the organic polyisocyanate Hylene W (also known as Mondur W) with excess 1,4-butane diol to provide the desired hydroxyl value.
  • Suitable copolymers are made by the solution copolymerization of monoethylenic monomers comprising 5% to 20% of 2-hydroxyethyl acrylate, the other monomers being selected to provide a glass transition temperature of 35° C.
  • the epoxy ester is preferably constituted by any diglycidyl ether of a bisphenol having a molecular weight less than about 500 which is reacted with an approximately stoichiometric proportion, based on 1,2-oxirane, of a fatty monocarboxylic acid, as previously described.
  • the preferred fatty acids are illustrated by linseed fatty acid, soya fatty acid, and the like, but lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid are also useful.
  • the diglycidyl ethers of a bisphenol are usually ethers of bisphenol A, but this class of commercially available bisphenol derivatives is well known.
  • the commercial product Epon 828 (Shell Chemical Company) will be used as illustrative.
  • a stoichiometric amount of a fatty monocarboxylic acid we mean enough acid to consume substantially all the oxirane functionality in the epoxy resin, and this embraces a small excess of acid providing an acid value in the ester of up to about 20, preferably less than 10.
  • the curing agents are themselves conventional in hydroxy-functional thermosetting coatings.
  • alkylated aminoplast resins preferably illustrated by hexamethoxymethyl melamine
  • blocked organic polyisocyanates such as 2-ethyl hexanol-blocked isophorone diisocyanate.
  • the selection of the curing agent and its proportion of use are both conventional.
  • the hydroxy-functional polyester should preferably constitute from 30% to 65% of the mixture of three reactive resins, the epoxy ester should preferably constitute from 15% to 30% on the same basis, and the balance of the mixture of resins will consist essentially of curing agent selected from alkylated aminoplast resins and blocked organic polyisocyanates. Based on the selection of an alkylated aminoplast resin, especially hexamethoxymethyl melamine, these are used in an amount of from 15% to 35%, based on the mixture of resins.
  • the solvents which are used to provide the desired low viscosity are of secondary significance and are subject to considerable variation.
  • the viscosity is preferably selected to enable air spray or electrostatic spray application.
  • Aromatic hydrocarbons, such as toluene, and commercial mixtures of aromatic solvents are useful, alone or in combination with aliphatic solvents. These are illustrated by acetone, methyl ethyl ketone, butanol, 2-ethoxy ethanol, 2-ethoxy ethanol acetate, butyl acetate, and the like. Of course, the aromatic component of the solvent mixture may be omitted.
  • the systems are desirably water-free and the solvents lack reactive hydrogen atoms.
  • the sealing compositions of this invention are desirably pigmented, typically to a pigment to binder ratio of 0.65:1, though this may vary from 0.3:1 to 0.9:1. It is preferred to use pigments having a low oil absorption capacity to minimize the increase in viscosity.
  • the coatings are usually applied by spray, as noted previously, in a thickness of from 3 microns to 1/16 inch. These coatings cure on baking, and the typical bake would be for 30 minutes at 280° F. Of course, one may increase the baking temperature by reducing the baking time. Also, when an organic isocyanate cure is used, the minimum practical baking temperature is lowered somewhat. For aminoplast resins, the minimum baking temperature is about 260° F. which may be lowered to about 230° F. in the presence of acid catalysts such as the disulfonic acids used in the examples.
  • neopentyl glycol 25.9 parts of neopentyl glycol is reacted in a hot melt with 35.4 parts of phthalic anhydride to consume the anhydride groups.
  • 35.0 parts of 2,2,4-trimethyl 1,3-pentanediol are then added at 150° C. along with 0.5% of dibutyl tin oxide esterification catalyst and 5% of xylol and esterification is carried out at 185° C. for one hour and then at 200° C. while removing water to provide an acid value of less than 6.
  • the temperature is then lowered to 180° C., and 3.7 parts of trimellitic anhydride is reacted in for 1 hour.
  • Xylol is then added to provide a 90% solution.
  • a corresponding solution in which the xylol is replaced by methyl ethyl ketone at 90% solids has a Gardner bubble viscosity of about Z 2 at 25° C.
  • a diglycidyl ether of bisphenol A having an average molecular weight of about 390 (Epon 828 of Shell Chemical Company may be used) is mixed with 7.2 parts of an epoxy novolac.
  • the epoxy novolac is prepared by reacting a phenolic novolac with epichlorohydrin and then dehydrohalogenating with sodium hydroxide.
  • the epoxy novolac contains about 3.6 phenol glycidyl ether groups per molecule, the phenol groups being connected to one another by a methylene bridge.
  • the epoxy resins are placed in solution in a 1:2 weight ratio mixture of xylol and methyl ethyl ketone and esterified with 54.7 parts of soya fatty acids to provide an ester product containing 87.5% solids.
  • a corresponding solution in which only xylol is used as the solvent and the solution has a solids content of 75% has a Gardner bubble viscosity of about Z 1 at 25° C.
  • the acid catalyst used in the above example desirably functions to lower the cure temperature.
  • Example 3 The solution of Example 3 was air sprayed onto a glass fiber reinforced polyester molding having a porous surface which normally causes porosity popping when topcoated and baked. The coating was then baked for 30 minutes at 280° F. Subsequent topcoating in the same manner as previously caused porosity popping did not result in this problem. Also, the finished product showed better water resistance and adhesion of the topcoat was improved.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Sealing Material Composition (AREA)
US06/515,029 1983-07-18 1983-07-18 Thermosetting coating compositions for the sealing of fiber reinforced plastics Expired - Fee Related US4526939A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US06/515,029 US4526939A (en) 1983-07-18 1983-07-18 Thermosetting coating compositions for the sealing of fiber reinforced plastics
CA000450820A CA1242829A (en) 1983-07-18 1984-03-29 Sealing fiber reinforced plastics
JP59102449A JPS6028435A (ja) 1983-07-18 1984-05-21 表面シ−ル用被覆組成物
EP84108176A EP0134493A3 (en) 1983-07-18 1984-07-13 Sealing fiber reinforced plastics

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Application Number Priority Date Filing Date Title
US06/515,029 US4526939A (en) 1983-07-18 1983-07-18 Thermosetting coating compositions for the sealing of fiber reinforced plastics

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US4526939A true US4526939A (en) 1985-07-02

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US (1) US4526939A (enrdf_load_stackoverflow)
EP (1) EP0134493A3 (enrdf_load_stackoverflow)
JP (1) JPS6028435A (enrdf_load_stackoverflow)
CA (1) CA1242829A (enrdf_load_stackoverflow)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4692383A (en) * 1986-07-21 1987-09-08 Ppg Industries, Inc. Polycarbonate based elastomeric coating compositions
US5098778A (en) * 1990-04-24 1992-03-24 General Electric Company Plastic based laminates comprising outer fiber-reinforced thermoset sheets, lofted fiber-reinforced thermoplastic sheets and a foam core layer
US5674565A (en) * 1993-06-23 1997-10-07 Cambridge Industries, Inc. Liquid thermoset sealers and sealing process for molded plastics
US20030077394A1 (en) * 2001-08-28 2003-04-24 Bradford Christophen J. Dual cure coating composition and process for using the same
US20030078316A1 (en) * 2001-08-28 2003-04-24 Bradford Christopher J. Dual cure coating composition and processes for using the same
US20030207956A1 (en) * 2001-08-28 2003-11-06 Balch Thomas C. Dual radiation/thermal cured coating composition
US6716891B1 (en) 1999-05-29 2004-04-06 Basf Coatings Ag Coating material that can be cured thermally or by actinic radiation, and its use
US20040132843A1 (en) * 2001-03-21 2004-07-08 Hubert Baumgart Method for coating microporous surfaces
US20050079293A1 (en) * 2002-02-15 2005-04-14 Hubert Baumgart Method for producing chromophoric and/or effect producing multilayer coatings
US6949591B1 (en) 1999-05-06 2005-09-27 Basf Coatings Ag Coating material which can be thermally cured and hardened by actinic radiation and use thereof
US20070021553A1 (en) * 2002-10-17 2007-01-25 Basf Coatings Aktiengesellschaft, Coating material which is thermally curable and curable by means of actinic radiation and method for coating microporous surfaces
US20090191407A1 (en) * 2008-01-18 2009-07-30 Lewarchik Ronald J Coatings providing low surface emissivity
CN107075295A (zh) * 2014-09-08 2017-08-18 佐敦集团 粉末涂料

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004105638A2 (en) 2003-05-27 2004-12-09 Spinalmotion, Inc. Prosthetic disc for intervertebral insertion

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US3291858A (en) * 1962-10-03 1966-12-13 Shell Oil Co Thermosetting resin based paints containing a polyester prepared by reacting phthalic anhydride, glycerol, and glycidyl esters of alpha-branched saturated monocarboxylicacids with either an amide-aldehyde or a phenolaldehyde resin
US4316940A (en) * 1980-03-21 1982-02-23 E. I. Du Pont De Nemours And Company High-solids polyester and aminoplast coating composition
US4362847A (en) * 1980-05-22 1982-12-07 Shell Oil Company Heat-curable thermosetting resin binder compositions comprising a non-acidic resinous compound, a non-acidic polyester cross-linking agent, and a transesterification catalyst

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Publication number Priority date Publication date Assignee Title
GB884031A (en) * 1959-02-19 1961-12-06 Shell Int Research Improvements in or relating to a process for the production of a water-emulsifiable epoxy-resin binder
US3748311A (en) * 1972-04-03 1973-07-24 Trw Inc Heterocyclic endo alicyclic end capped resins
CA1114576A (en) * 1977-07-11 1981-12-22 Sigurdur I. Arnason In-mold coating of sheet molding compound moldings

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3291858A (en) * 1962-10-03 1966-12-13 Shell Oil Co Thermosetting resin based paints containing a polyester prepared by reacting phthalic anhydride, glycerol, and glycidyl esters of alpha-branched saturated monocarboxylicacids with either an amide-aldehyde or a phenolaldehyde resin
US4316940A (en) * 1980-03-21 1982-02-23 E. I. Du Pont De Nemours And Company High-solids polyester and aminoplast coating composition
US4362847A (en) * 1980-05-22 1982-12-07 Shell Oil Company Heat-curable thermosetting resin binder compositions comprising a non-acidic resinous compound, a non-acidic polyester cross-linking agent, and a transesterification catalyst

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4692383A (en) * 1986-07-21 1987-09-08 Ppg Industries, Inc. Polycarbonate based elastomeric coating compositions
US5098778A (en) * 1990-04-24 1992-03-24 General Electric Company Plastic based laminates comprising outer fiber-reinforced thermoset sheets, lofted fiber-reinforced thermoplastic sheets and a foam core layer
US5674565A (en) * 1993-06-23 1997-10-07 Cambridge Industries, Inc. Liquid thermoset sealers and sealing process for molded plastics
US6949591B1 (en) 1999-05-06 2005-09-27 Basf Coatings Ag Coating material which can be thermally cured and hardened by actinic radiation and use thereof
US6716891B1 (en) 1999-05-29 2004-04-06 Basf Coatings Ag Coating material that can be cured thermally or by actinic radiation, and its use
US20040132843A1 (en) * 2001-03-21 2004-07-08 Hubert Baumgart Method for coating microporous surfaces
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US20090191407A1 (en) * 2008-01-18 2009-07-30 Lewarchik Ronald J Coatings providing low surface emissivity
CN107075295A (zh) * 2014-09-08 2017-08-18 佐敦集团 粉末涂料

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JPS6028435A (ja) 1985-02-13
EP0134493A3 (en) 1985-12-18
EP0134493A2 (en) 1985-03-20
CA1242829A (en) 1988-10-04
JPH0427258B2 (enrdf_load_stackoverflow) 1992-05-11

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